Resinous composition



Patented Feb. I, 1944 ansmous ooMrosmoN Ferdinand P. Otto and Orland M.Reid, Woodbury, N. J., assignors to Socony-Vacuum Oil Company,Incorporated, New York, N. 1., a corporation of Ncw York No Drawing.Application December 19, 1941,

Serial No. 423,580

(01. zsoj-si) 4 Claims.

This invention has reference to a resinous composition of matter and isparticularly concerned with a hard resin derived by mono-aikylation ofaromatic bodies.

In one respect, the present invention is related to the disclosure ofPatent No. 2,191,498, issued February 27, 1940, to 0. M. Reifi and thecopending application of O. M. Reid and J. J.

Giammaria, Serial No. 427,588, filed Januar 21,

1942. Both of said disclosures are directed to aromatic compounds andmixtures of aromatic compounds which have been substituted with longchain aliphatic radicalsby a Friedel-Crafts reaction. In both instances,the aliphatic radical is preferably derived from petroleum wax. In theserespects the present disclosure resembles the earlier disclosures notedabove. As respects properties of the compositions concerned, the presentinvention relates to material of widely different nature. The productsor the said patent are viscous liquids, soluble in lubricating oil,obtained by reaction of aromatic with chlorinated wax of about 14%chlorine content in such proportions as to polyalkylate the aromatic.The compositions described in the said application areplastic,rubber-like masses insoluble in hydrocarbon oils which result fromreaction of an excess of chlorinated wax or high chlorine content (morethan 25%) with aromatic compounds.

The products of this invention are hard resinous bodies soluble invarnish resin solvents and are derived by reacting highly chlorinatedwax, or other suitable aliphatic hydrocarbons, containingfrcm about 40%to about 60% of .chlorine with aromatic compounds and mixtures of suchcompounds in proportions to theoretically result in mono-alkylation fthe aromatic. Preferably the aromatic reactant is used in substantialexcess with respect to the chlorine content. By following the teachingsof this invention as outlined above and described in greater detailbelow, the desired hard resin is obtained in a form admirably suited tothe formation of fine coating compositions and for other purposes thatwill be apparent to those skilled in the art.

0f the two reactants, the chlorinated aliphatic seems to be the moreimportant in afiecting the characteristics of the final product. Goodresults are obtained with aromatic compounds in general by reaction withaliphatic hydrocarbons having upwards of about carbon atoms, whichhydrocarbons have been chlorinated to the extent of about 40% to 60% byweight. Preferably an aliphatic compound of about 50% chlorine contentis employed. Some variations in properties of the resins are noted withvariations in the character of the aromatic used but the generalproperties or a hard resin are found within the above limits ofchlorination when the proportions of reactants are. such that there ispresent in the reaction mixture at least one moi of aromatic compoundfor each moi of combined chlorine in the chlorinated aliphatic. It isunderstood, of course, that other halogens than chlorine are availablefor the purposes of the invention and chlorine is discussed here asexemplary because it is the halogen generally used for the presentpurpose.

Although aliphatic compounds and mixtures of relatively low molecularweight, about 10 carbon atoms, are suitable; best results are obtainedby the use or chlorinated petroleum waxes. Such waxes often contain somecomponents of as few as 15 carbon atoms but the predominant portion ofany such wax is usuall composed of aliphatic hydrocarbons of or morecarbon atoms with an average of about 24 carbon atoms and an averagemolecular weight of about 350.

The hard, resin compositions derived from the reaction of chlorinatedwax with aromatic compounds, might be more aptly described as arylatedwaxes because of their high aromatic content.

Hard resins derived from phenol for instance,

have a combined phenol content of about 40%, the remainder of themolecule consisting 01' combined wax. A trace of chlorine is ordinarilypresent from incomplete reaction, but is not necessary for the formationof a hard resin.

The compositions may be represented by the following general formulaewhich is not an attempt to give, however, an exact representation of themolecule. For simplicity the different aromatic nuclei are representedby the phenyl radicals.

group will be attached in some cases to more than one carbon of the samewax group, particu- Zinc dust (for decolorizing) larly in reactions witharomatic compounds of the condensed nuclei and polycyclic type.

The foregoing conclusions are substantiated by the molecular'weights ofthe wax aromatic resins which were determined by the boiling pointmethod, using benzene as solvent. The following results were obtained.

Some chain formation would be expected to occur in the reaction ofaromatic compounds with highly chlorinated waxes, in which case thefollowing representation would be applicable, but the low molecularweights of the resins indicate little chaining of the arylated waxmolecules.

iLQQQQQ Q Q Q Q Q The resins consist apparently of a mixture of thecompounds represented by Formulas 1, 2 and 3. Because of the complexityof the mixtures, no attempt has been made to separate the resins intotheir constituents.

The dili'erent aromatic compounds are not equivalent in respect to thedegree of chlorination of the wax required to produce a resin of thesame degree of hardness and same melting point. Further, each aromaticcompound can be reacted with chlorwax of variable chlorine content toobtain products of different degrees of hardness and different meltingpoints. For a chlorinated wax of different chlorine content, a harderresin is derived from phenol than from aromatic hydrocarbons or aromaticothers. In the following examples, a proportion of reactants is givenwherebya resin of desirable degree of hardness and suitable meltingpoint can be formed from different aromatic compounds. Ex amples only ofunsubstituted hydroxyaromatic and aromatic hydrocarbons and aromaticethers are given. Aromatic compounds containing low molecular weightalkyl substituents as in the case of toluene, xylene andmethyl-naphthalene require reaction with chlorinated wax of higherchlorine content to obtain a resin of comparable hardness.

EXAMPLE I WAX PHENOL RESIN Paraflin wax of A. S. T. M. melting point ofabout 126 F. and of average molecular weight of about 350 is melted, anda current of chlorine is introduced at a temperature of about 200 F.until about 45% by weight of chlorine is absorbed. The rate ofabsorption of chlorine can be materially increased by carrying out thereaction in the presence of light. The phenol is then introduced,followed by gradual addition of the anhydrous A101: at a temperature ofabout 60 C. with rapid stirring. The temperature of the mixture isgradually raised to about 175 C. during a 2-hour period and held at thispoint until the evolution of HCl is complete, which will require about 4hours.

The color of the reaction mixture can be lightened by the reducingaction of zinc dust and dilute hydrochloric acid. This reduction iscarried out by adding 300 grams of zinc dust and 100 c. c. of water atabout 90 C. and stirring the mixture several hours. In order to obtain aproduct of lighter color, it is desirable to add additional hydrochloricacid and continue the reduction several hours longer. As an aid tostirring the reaction mixture, it is desirable to add about 500 c. c. ofbenzene before carrying out the reduction procedure. The reactionmixture is then filtered to remove excess zinc, followed by waterwashing to remove acid, zinc chloride and aluminum chloride and thentopping by heating to about 180 C. under diminished pressure to removesolvent and unreacted phenol. The product obtained is a light brown,hard resin 01 about phenol content.

This reaction procedure is applicable to the production of hard resinsfrom hydroxyaromatic compounds in general. In the preparation of hardresins by the reaction of chlorinated wax with aromatic hydrocarbons andaromatic ethers, essentially the same reaction procedure is used. LessAlCh is required for the reaction. In the formation of hard resins fromthe following reaction mixtures, a top reaction temperature of about150. C. is used in carrying out the Friedel-Crafts reaction. In the caseof aromatic hydrocarbons boiling below 150 C., the Friedel- Craftsreaction is carried out at the boiling point of the aromatic compounds.Benzene, for instance, is converted to a hard resin by reaction withchlorinated wax at 80 C. Reaction mixtures for several resins within thescope 01' the invention are set out below.

EXAMPLEII Wax Benzene Rnsm Grams Chlorinated wax of 50% chlorine content150 Benzene in excess or amount required for reaction) 330 AlCh (20% byweight based on chlorwax) 30 Zinc dust (for decolorizing) 100 EXAMPLEIII WAX Drrnnm Resm Grams Chlorinated wax of 50% chlorine content 150Diphenyl (50% in excess of amount required Wax Nara-mucus Rnsm GramsChlorinated wax of 50% chlorine content Naphthalene (100% in excess ofamount required for reaction) 520 AlCls 28 Zinc dust (for decolorizing)100 EXAMPLE V Wax Drrnnmoxmr: Rnsm Grams Chlorinated wax of 50% chlorinecontent 100 Diphenyloxide (50% inexcess of amount re quired forreaction); 348 A1013 Zinc dust 100 EXAMPLE VI RESIN FROM REACTION orCHLORINATED STODDARD SOLVENT wrrn PHENOL Reaction mixture GramsChlorinated Stoddard solvent-50% chlorine content Phenol (100% in excessof amount required for reaction) 404 Aluminum chloride (30% based onweight of chlorinated aliphatic) 45 Zinc dust 100 To a reaction mixtureconsisting .of the chlorinated Stoddard solvent and phenol at 55 C. isadded 45 grams of aluminum chloride. The temperature is then graduallyraised to 175 C. and held there until the evolution of hydrogen chloridepractically ceases, which will require about 2 hours. The reduction stepthen follows, consisting of dilution with 300 cc. of Stoddard solventand the addition of zinc dust and 30 cc. of water, followed by refluxingthe mixture for two hours. At this point, it is desirable to add 100 cc.of concentrated hydrochloric acid and conpale yellow by procedures setout below.

EXAMPLE VII Grams Wax'diphenyl oi Example III 100 Dimrnnp 50o Raneynickel 20 The resin is'dissolved in approximately five times its weightof dioxane and then placed in a high pressure shaker-bomb along with 20%by weight of .Raney nickel catalyst; The catalyst is prepared accordingto Covert and Adkins, J. A. C. S. 54, 4116 (1932). The initial pressureof hydrogen in the bomb is 1500 lbs/sq. inch. The temperature is thenraised to 500 F. and held there for a period or 7 hours during whichtime the pressure remains at 2700 lbs/sq. inch. After cooling, thereaction mixture is removed from the bomb and filtered to removecatalyst.

This is followed by topping to 175 C. under diminished pressure (5 mm.)to remove the solvent and to obtain the finished product.

EXAMPLE VIII Grams Wax phenol of Example I. Dioxane 500 Raney nickel 20The treatment is conducted in substantially the same fashion as inExample VII.

The alkylated aromatic compounds will undergochemical reactions of whichthe parent aromatic compounds are capable, but with for-- mation ofproducts of different physical characteristics. The hard resins can beimproved, for instance, by reaction with formaldehyde and otherresinifying agents.

The hard resins vary from brown to pale yellow or colorless compoundsdepending upon the degree of reduction with hydrogen. The resins aresoluble in varnish resin solvents and have been found to give highlydesirable coatings.

Although the resin forming reaction has been described as conducted withthe use of an aluminum chloride catalyst, it will be understood that anysuitable alkylation catalyst may be used,

pounds other than aromatics. The term "aromatic material is accordinglyused in the claims to comprehend these aromatic compositions within thecope of the invention, it being understood that proportions recitedrelate only to'the reactive aromatic compounds and do not includediluents, impurities and the like.

We claim:

1. A hard resinous light-colored composition of matter formed byreacting a phenol with a chlorinated petroleum wax containing about 40%to about 60% by weight of chlorine in a mol ratio of not less than onemol of phenol for each mol of combined chlorine in the presence of aFriedel- Crafts type catalyst, adding metallic zinc and water toreaction product to decolorize the same and catalytically hydrogenatingthe product from treatment with zinc and water.

2. A hard resinous composition of matter formed by reacting a phenolwith a chlorinated petroleum wax containing about 40% to about 60% byweight of chlorine in a mol ratio of not less than one mol of phenol foreach mol of combined chlorine in the presence of a Friedel- Crafts typecatalyst.

3. A hard resinous light-colored composition of matter formed byreacting a phenol with a chlorinated petroleum wax containing about 50%by weight of chlorine in a mol ratio of not less than one mol ofphenolfor each mol of combmed chlorine in the presence of a Friedel-Craitstype catalyst, adding metallic zinc and water to reaction product todecolorize the same and catalytically hydrogenating the product fromtreatment with zinc and water.

4. A hard resinous composition of 'matter formed by reacting a phenolwith a chlorinated petroleum wax containing about 50% by weight ofchlorine in a mol ratio of not less than one mol of phenol for each molof combined'chlorine m the presence of a Friedel-Crafts type catalyst.

, FERDINAND P. OTTO.

ORLAND M. REIEF.

